In recent years, attempts have been made to use various functions of coating films formed by providing liquid compositions—such as solutions, slurries or pastes, which are equipped with various functions, respectively, and may hereinafter also be collectively referred to as “slurries”—as functional coating formulations and applying the functional coating formulations. Such attempts are under way in various fields such as paints, inks, coating agents, magnetic materials, ceramics, building materials, adhesives, liquid crystal color filters, pharmaceuticals, electronic materials, and electricity storage devices.
For example, a paste-form, conductive coating formulation composed of a conductive material, binder resin, curing agent, solvent and the like is used as a conductive adhesive, conductive paint, conductive ink or the like (Non-patent Document 1). A coated, magnetic recording medium such as an audio tape, video tape or flexible disk is manufactured by applying, onto a base film of a polyester or the like, a magnetic coating formulation with magnetic particles of submicron size evenly dispersed in a polymer solution. Further, electrodes for a lithium ion secondary cell are each prepared by mixing an active material, conductive material and binder to prepare a slurry, coating the slurry onto a collector foil, and then drying it (Non-patent Document 2).
To allow each of such various functional coating formulations as described above to fully exhibit its functionality, the coating film to be formed is required to be equipped with durability and high adhesiveness to a base material. In other words, it is essential conditions that the coating formulation is in a state appropriate for the exhibition of the functionality and can form a coating film having high adhesiveness to the base material and durability. As solvents (dispersion media) for such coating formulations, nonaqueous (organic solvent-based) solvents, which exhibit high compatibility with base materials and can be readily dried, are overwhelmingly advantageous, and as a matter of fact, have been used widely.
However, organic solvents are generally high in volatility. Accordingly, they are not only high in environmental load but also required to take genotoxicity into consideration, and therefore, still involve problems in safety and workability. In recent years, there is an increasing concern about the protection of environment and the prevention of health hazards in many industrial fields. There is, hence, an increasing demand toward VOC reductions, solventless coating and the like in connection with the use of organic solvents involving such problems as described above, leading to an outstanding requirement to switch to products that are friendly to the environment and people.
As products friendly to the environment and people, water-based products or products made from raw materials of biological origin are drawing attention. These products are expected to become part of solventless or post-petroleum products. Various problems, however, arise if water is used as a solvent in place of an organic solvent. For example, a water-based coating formulation involves a problem in that it is inferior in film-forming ability to an organic solvent-based coating formulation. Further, a slurry-form, water-based coating formulation with a filler contained therein is accompanied by a problem in that the filler tends to agglomerate in the slurry when it is in a charged state, and moreover, the filler is prone to settling due to a large difference in specific gravity between the solvent and the filler, thereby raising another problem in that its even dispersion is difficult. In addition, it is not easy to find raw materials of biological origin, which exhibit film-forming ability and dispersing ability and can replace conventional raw materials of petroleum origin.
Upon attempting the dispersion and stabilization of a filler in a water-based slurry, various methods may be contemplated including the use of a dispersant, the surface treatment, microencapsulation and ultrasonic treatment of the filler, and the introduction of polar groups into a polymer. Among these methods, the use of the dispersant is advantageous when the simplification of the production method and coating system and the cost matter are taken into account. As the dispersant for use in the water-based slurry, a polycarboxylate salt or phosphate amine salt used in the field of paints (Non-patent Document 3), a polyacrylamide as a high-molecular dispersant (Non-patent Document 4), or the like is conceivable. When a reduction in environmental load is taken into consideration, however, the dispersant may preferably be a substance of natural origin, which is friendly to the environment. A proposal has been made about the use of carboxymethylcellulose as a water-based dispersant upon production of each electrode for a nonaqueous electrolyte secondary cell (Patent Document 1). Concerning carboxymethylcellulose, however, there is still a room for an improvement in its dispersing effect. On the other hand, the use of a petroleum-based binder resin is needed to form a strong coating film. There is, accordingly, an outstanding desire for a utilization technology of a natural polymer that, although it is a substance of biological origin, can exhibit adhesiveness which is by no means inferior to that available from the use of a petroleum-based binder resin.
As an expected application of the water-based slurry, a coating formulation for electrode plates in electricity storage devices such as secondary cells or capacitors is considered. The demand for these electricity storage devices has been significantly growing in recent years. Each electrode plate is an electrode plate member, that includes unit members such as an electrode layer and collector integrated therein and gives significant effects on the performance of an electricity storage device. Proposals have been made to permit the production of an electrode plate in the form of a thinner film with larger area such that an electricity storage device can be provided with an extended charge-discharge cycle life and an increased energy density. For example, Patent Documents 2 and 3 disclose positive electrode plates, each of which is obtained by dispersing or dissolving a positive-electrode active material such as a metal oxide, sulfide or halogenide, a conductive material and a binder in an appropriate solvent to prepare a paste-form coating formulation, and then applying the coating formulation onto a surface of a collector formed of a foil of a metal such as aluminum to form a coating film layer.
A negative electrode plate for a cell or a polarizable electrode plate for a capacitor is obtained by mixing an active material such as a carbonaceous material with a solution of a binder in a suitable solvent to obtain a paste-form coating formulation and then applying the coating formulation onto a collector to form a coating film layer. The binder employed to prepare the coating formulation is required inter alia to be electrochemically stable to a nonaqueous electrolyte and to be free from dissolution into the electrolyte for the cell or capacitor, to remain free from substantial swelling by the electrolyte, and further to be soluble in a certain solvent.
On the other hand, it is practiced to form a protective film on a surface of a metal material such as aluminum, as a base metal material of a collector, by coating a solution of one of various resins. The resulting protective film is excellent in the adhesiveness to the metal surface, but is accompanied by a problem in that its durability to an organic solvent is insufficient.
The coating film layer of the electrode plate for the cell or capacitor, said coating film layer having been obtained by applying the above-described paste-form coating formulation onto a collector, is accompanied by problems in that its adhesiveness to the collector and its flexibility are insufficient. In addition, the coating film layer has a high contact resistance to the collector, and may undergo peeling, flaking, cracking and/or the like upon assembly of the cell or capacitor or upon charging and discharging the same.
As described above, the conventional cell or capacitor is accompanied by the problems of the poor adhesion between the electrode layer and the collector (substrate) and the high internal resistance between the electrode layer and the collector. A variety of coating formulations have been proposed to solve these problems. By coating film layers formed with the various coating formulations so proposed, the problem of poor adhesiveness has been increasingly lessened. However, still higher resistance is produced between the electrode layer and the collector, so that none of these coating formulations have led to a solution to the problems yet. In recent years, there is also a demand for a manufacturing method, which has paid due consideration to the environment, for the above-mentioned electricity storage devices and their related products. There is hence a demand for a coating formulation making use of components, which are low in environmental load.